Fire-resistant coating material

ABSTRACT

The present invention is a fire-resistant paint containing an epoxy resin, a hardener, and an inorganic filler wherein 
     {circle around (1)} for the total of 100 weight parts of the epoxy resin and the hardener, 
     {circle around (2)} 200-500 weight parts of the inorganic filler, chosen from a group consisting of neutralized thermally expandable graphite, metal carbonate, and a hydrated inorganic compound is contained; 
     {circle around (3)} for the inorganic filler, at least 15-400 weight parts of neutralized thermally expandable graphite is contained; and 
     {circle around (4)} the viscosity of the fire-resistant paint is 1-1,000 ps as measured by a B-type viscometer. The fire-resistant paint of the present invention has particularly remarkable fire resistance, and can be used in a wide range of applications.

FIELD OF THE INVENTION

This invention relates in general to a fire-resistant paint, and moreparticularly to a fire-resistant paint which is used to improve thefire-resistance of building materials by means of coating.

BACKGROUND OF THE INVENTION

In the field of building materials fire-resistance has an importantmeaning. Recently, as the applications of resin materials expand, resinmaterials are widely used for building materials and resin materialswith fire-resistant properties are desired.

For such fire-resistance properties, not only the resin material itselfis required to resist combustion, but the resin material is alsorequired to protect the building material from flames when it is used asa fire-resistant coating material on building materials. Although theintrinsic nature of resin materials is to burn and melt, they must notburn or melt and come off when they are used as fire-resistantmaterials.

A fire-resistant coating is sometimes applied in advance on beams,columns, and such because of the desire to reduce the processes on theconstruction site. However, coating cannot be applied in advance onbeam-column joints, junctions, and metal fixtures for installing outerwalls and such. These parts have to be done on the construction site.For application on the construction site, painting such as by sprayingis easier to implement than coating with a coating material in a sheetor board form. Painting is also more preferable when coating a structurewith a complex form.

For a spray type fire-resistant coating, rockwool spraying is common,but this requires a thicker coating to satisfy the fire-resistantproperties. Fire-resistant paint is widely known to give a thinnerfire-resistant coating. However, conventional fire-resistant paint hasproblems in that the residue after heat expansion is fragile and so theresidue after expansion may come off, and also that it containspolyhydric alcohol which has a high solubility in water, resulting inwater resistance problems and requiring a top coat layer on the paintsurface.

In view of what is described above, a fire-resistant paint with both athin coating thickness and a solid residue after expansion is desired.The object of the present invention is to provide a heat expandingfire-resistant paint which manifests particularly prominentfire-resistant performance by leaving a residue with sufficient shaperetaining properties after combustion, is safe for human body, and iseasily coated on any part.

The problems which have been solved by the present invention aredescribed below by referring to specific conventional technology.

{circle around (1)} Japanese unexamined patent publication Tokkai Sho58-2356 and Tokkai Sho 57-67673 discloses fire protective butyl rubberpaint. When lamination with other components is done after butyl rubberpaint is applied and air dried, fasteners such as screws and/or nailshave to be used for securing, which causes cracks and/or fissuresresulting in reduced fire-resistance performance. In order to improve onthis issue, Tokkai Sho 58-2356 and Tokkai Sho 57-67673 disclose a paintwhich uses butyl rubber for the resin binder. However, antimonytrioxide, in the case of Tokkai Sho 57-67673, and asbestos and/orhalogen, in the case of Tokkai Sho 58-2356, have to be added forsufficient fire-resistance performance. There is a problem in that thesesubstances can have adverse effects on the human body duringmanufacturing, applying, burning, etc. On the other hand, thefire-resistant paint of the present invention can achieve superiorfire-resistant performance using substances which are safe to the humanbody.

{circle around (2)} Japanese examined patent publication Tokko Sho63-7238 illustrates a foaming fire-protective composition composed ofthermally expandable graphite and a phosphorus compound. A low molecularweight hydrocarbon (or derivative) is used to give a putty form to thiscomposition. When this is used on a vertical site and heated, saggingoccurs before foaming due to its insufficient retaining propertyresulting in insufficient fire-protective performance. On the otherhand, the fire-resistant paint of the present invention can be assuredto have a sufficient retaining property by proper selection of the resinbinder so there is no sagging before foaming when used on a verticalsite and heated. Therefore, it can manifest sufficient fire-resistantperformance regardless of heating conditions.

{circle around (3)} Tokkai Hei 5-70540 illustrates a paint which usesthermally expandable graphite, a phosphorus compound, a polyhydricalcohol, and a nitrogen-containing compound-based foaming agent, withurethane resin for the binder. However, since a polyhydric alcohol whichis highly soluble in water is used, there is a problem in terms of waterresistance of the paint, requiring top coating. When a polyhydricalcohol is not used, the residue does not have sufficient strength.

{circle around (4)} Tokkai Hei 9-227716 and Tokkai Hei 10-7838 propose afire-resistant resin composition which leaves a firm residue afterexpansion. However, because of its viscosity, it is hard to use as acoating paint.

{circle around (5)} Publication WO98/31730 of PCT application(PCT/JP97/02258) illustrates a thermally expandable fire-resistantmolded sheet. However, since this is a molded sheet, covering specialsites on a building component is difficult.

{circle around (6)} Tokkai Hei 9-183978 illustrates a foamingcomposition for a fire-resistant paint which is an acrylic resincontaining low temperature expandable graphite, a phosphoric acidcompound, melamine, and a polyhydric alcohol. However, since apolyhydric alcohol which is highly soluble in water is used, there is aproblem in terms of water resistance of the paint, requiring topcoating. When a polyhydric alcohol is not used, the residue does nothave sufficient strength.

Compared with these, the fire-resistant paint of the present inventioncan be applied on any site, can ensure sufficient residue strengthwithout using a polyhydric alcohol, and has no problems in terms ofwater resistance.

DISCLOSURE OF THE INVENTION

(1) The first (claim) of the present invention is a fire-resistant paintcontaining an epoxy resin, a hardener, and an inorganic filler wherein

{circle around (1)} for the total of 100 weight parts of the epoxy resinand the hardener,

{circle around (2)} 200-500 weight parts of the inorganic filler, chosenfrom a group consisting of neutralized thermally expandable graphite,metal carbonate, and a hydrated inorganic compound is contained;

{circle around (3)} for the inorganic filler, at least 15-400 weightparts of neutralized thermally expandable graphite is contained; and

{circle around (4)} the viscosity of the fire-resistant paint is 1-1,000ps as measured by a B-type viscometer.

(2) The second (claim) of the present invention is a fire-resistantpaint containing an epoxy resin, a hardener, and an inorganic fillerwherein

{circle around (1)} for the total of 100 weight parts of the epoxy resinand the hardener,

{circle around (2)} 15-400 weight parts of neutralized thermallyexpandable graphite and a phosphorus compound is contained;

{circle around (3)} the weight ratio between the neutralized thermallyexpandable graphite and the phosphorus compound is (thermally expandablegraphite/phosphorus compound)=0.01-9;

{circle around (4)} 10-400 weight parts of a metal carbonate and/orhydrated inorganic compound is contained;

{circle around (5)} the total amount of the neutralized thermallyexpandable graphite and phosphorus compound, and the metal carbonateand/or hydrated inorganic compound is 200-500 weight parts; and

{circle around (6)} the viscosity of the fire-resistant paint is 1-1,000ps as measured by a B-type viscometer.

(3) The third (claim) of the invention is a fire-resistant paintcontaining butyl rubber or isobutylene rubber and an inorganic fillerwherein

{circle around (1)} Flory's viscosity-average molecular weight of thebutyl rubber or isobutylene rubber is 5,000-4,000,000; and

{circle around (2)} for 100 weight parts of the butyl rubber orisobutylene rubber,

{circle around (3)} 200-500 weight parts of the inorganic filler, chosenfrom a group consisting of neutralized thermally expandable graphite,metal carbonate, and a hydrated inorganic compound is contained;

{circle around (4)} for the inorganic filler, at least 15-400 weightparts of neutralized thermally expandable graphite is contained; and

{circle around (5)} the viscosity of the fire-resistant paint is 1-1,000ps as measured by a B-type viscometer.

(4) The fourth (claim) of the invention is a fire-resistant paintcontaining butyl rubber or. isobutylene rubber and an inorganic fillerwherein

{circle around (1)} Flory's viscosity-average molecular weight of thebutyl rubber or isobutylene rubber is 5,000-4,000,000; and

{circle around (2)} for 100 weight parts of the butyl rubber orisobutylene rubber,

{circle around (3)} 15-400 weight parts of neutralized thermallyexpandable graphite and a phosphorus compound is contained;

{circle around (4)} the weight ratio between the neutralized thermallyexpandable graphite and the phosphorus compound is (thermally expandablegraphite/phosphorus compound)=0.01-9;

{circle around (5)} 10-400 weight parts of a metal carbonate and/orhydrated inorganic compound is contained;

{circle around (6)} the total amount of the neutralized thermallyexpandable graphite and phosphorus compound, and the metal carbonateand/or hydrated inorganic compound is 200-500 weight parts; and

{circle around (7)} the viscosity of the fire-resistant paint is 1-1,000ps as measured by a B-type viscometer.

Also, the present invention is the following fire-resistant paintsderived from any of the aforementioned first-fourth inventions, as wellas base materials which are coated with the fire-resistant paints.

(5) Said fire-resistant paint wherein the average particle size of saidneutralized thermally expandable graphite is 20-200 mesh.

(6) Said fire-resistant paint wherein said metal carbonate is one ormore metal carbonates chosen from a group consisting of calciumcarbonate, magnesium carbonate, strontium carbonate, barium carbonateand zinc carbonate.

(7) Said fire-resistant paint wherein said hydrated inorganic compoundis one or more hydrated inorganic compounds chosen from a groupconsisting of calcium hydroxide, magnesium hydroxide, aluminumhydroxide, and hydrotalcite.

(8) The fire-resistant paint of the aforementioned first or secondinvention wherein said fire-resistant paint is a no-solvent paint.

(9) The fire-resistant paint of the aforementioned third or fourthinvention wherein said fire-resistant paint is a solvent-based oremulsion-based paint containing an organic solvent or water.

(10) A fire-resistant paint-coated base material coated with the paintfilm by applying the aforementioned fire-resistant paint on the basematerial.

(11) Said fire-resistant paint-coated base material wherein said basematerial is non-woven fabric, woven fabric, film, plastic board, woodenboard, ceramic board, rockwool board, plaster board, or metal board.

THE BEST MODES OF THE EMBODIMENTS

The configuration of the present invention is described in detail below.

(1) The First and the Second Invention

The fire-resistance performance of the fire-resistant paint of thepresent invention manifests synergistically by combining an epoxy resin,a hardener, and a specific inorganic filler containing neutralizedthermally expandable graphite in specific blend ratios. Although theaction mechanism is not clear, the cross- inked structure of the epoxyresin contributes to the strength of the fire-resistant paint film and,when heated by fire, the thermally expandable graphite forms a heatinsulating layer after expansion to prevent heat transfer. When thishappens, it is believed that the epoxy resin is carbonized andcontributes as a heat insulating layer after expansion wherein thecross-linked structure of the epoxy resin works favorably for the shaperetaining properties following the heat expansion. The inorganic fillerincreases the heat capacity when heated, and the addition of thephosphorus compound further improves the shape retaining ability of theinorganic filler and the heat insulating layer after expansion.

Select ion of the epoxy resin used in the present invention is notlimited in particular, and prior art epoxy resins used in paints can beused. Examples of the glycidyl ether type with two functional groupsinclude the polyethylene glycol type, polypropylene glycol type,neopentyl glycol type, 1,6-hexanediol type, trimethylol propane type,bisphenol A type, propylene oxide-bisphenol A type, hydrogenatedbisphenol A type, and bisphenol F type. Examples of the glycidyl estertype include the hexahydro phthalic anhydride type, tetrahydro phthalicanhydride type, dimeric acid type, and p-oxybenzoic acid type. Examplesof the glycidyl ether type with multiple functional groups include thephenol novolac type, orthocresol novolac type, DPP novolac type, anddicyclopentadiene-phenol type. These can be used independently or incombinations of two or more.

The epoxy resin used in the present invention manifests heat insulatingproperties and shape retaining properties in the carbonized layer afterheating. Within the range which does not affect this effect, otherresins can be added as a resin component. A preferable amount of theother resins to be added is up to five times the weight of the epoxyresin. If the amount exceeds this range, then the effect of the presentinvention may not manifest.

For the hardener used in the present invention, hardeners that arecommonly used as epoxy resin hardeners can be used. Examples of thepolyaddition type include a poly amine, acid anhydride, poly phenol, andpoly mercaptane. Examples of the catalyst type include a tertiary amine,imidazole (and its derivatives), and Lewis acid complex. For the amountof the hardener to be added, any amount within the range in which theepoxy resin hardens can be used. Generally, 80-10 wt % is used for 20-90wt % of the epoxy resin.

(2) The Third and the Fourth Invention

The fire-resistance performance of the fire-resistant paint of thepresent invention manifests synergistically by combining butyl rubber orisobutylene rubber with a specific molecular weight and specificinorganic filler containing neutralized thermally expandable graphite inspecific blend ratios. Although the action mechanism is not clear, thebutyl rubber or isobutylene rubber with a specific molecular weightcontributes to the properties of the fire-resistant paint film, and,when heated by fire, the thermally expandable graphite forms a heatinsulating layer after expansion to prevent heat transfer. When thishappens, it is believed that the butyl rubber or isobutylene rubber witha specific molecular weight is carbonized and contributes as a heatinsulating layer after expansion and works favorably for the shaperetaining properties after the heat expansion. The inorganic fillerincreases the heat capacity when heated, and the addition of thephosphorus compound further improves the shape retaining ability of theinorganic filler and the heat insulating layer after expansion.

The butyl rubber and/or isobutylene rubber used in the present inventionare described below. In the fire-resistant paint of the presentinvention, butyl rubber and/or isobutylene rubber are used for thebinder resin. By using sticky butyl rubber or isobutylene rubber,lamination and temporary fixation with other components such as a waterprotective sheet and metal can be easily done even after the paint isdried, and therefore the number of the mounting components can bereduced, or assembly can be done without any mounting components,resulting in better workability. When nails or screws are used forfixation, no cracks develop around them because the paint is flexible.Also, since the sealing properties are good, the homogeneity of thepaint film thickness is not affected either.

The Flory's viscosity-average molecular weight of the butyl rubber orisobutylene rubber must be 5,000-4,000,000, preferably 10,000-1,000,000,and more preferably 200,000-500,000. If the Flory's viscosity-averagemolecular weight is less than 5,000, then the aggregation force isinsufficient and therefore sufficient paint film strength cannot beobtained. Also, since the flowability at normal temperatures is high,there may be sagging over time when painting is done on a verticalsurface. If the Flory's viscosity-average molecular weight is more than4,000,000, then the dissolving rate into the solvent slows down,resulting in lower productivity, and a high viscosity may affect theworkability as a paint. Furthermore, if the Flory's viscosity-averagemolecular weight is 200,000 or more, then chipping is easy andproductivity improves. If the Flory's viscosity-average molecular weightis 500,000 or less, the suitable range of stickiness, which will bediscussed later, can be ensured by the binder resin alone.

When considering lamination of the paint film and another componentafter drying, the suitable range of stickiness, based on JIS Z 0237, is500 gf/25 mm-6,000 gf/25 mm of peeling force when the prepared paintfilm is pasted on a galvanized iron sheet and peeled off from thegalvanized iron sheet after one hour at a velocity of 300 mm/min in the90 degree direction. If the peeling force is less than 500 gf/25 mmthen, although there is no problem for temporary securing, supportinganother component is difficult. If the peeling force is more than 6,000gf/25 mm, then no change/modification is possible if inadvertent pastinghappens during the lamination process, resulting in reducedproductivity. The stickiness can be adjusted by the addition of polybutene, tackifier, etc., as well.

The butyl rubber or isobutylene rubber with the as aforementionedviscosity-average molecular weight range can be used independently or incombination of two or more.

Furthermore, cross-linking or vulcanization can be done within the rangewhich does not impede the fire-resistance performance and solubility inthe solvent.

Selection of the methods for cross-linking or vulcanization of theaforementioned butyl rubber is not limited in particular. A method whichuses a cross-linking agent is commonly used. Examples of thecross-linking agent include a combination of sulfur, dimethyl carbamate,and thiazole, a combination of morpholine disulfide and dithiocarbamate; and quinone dioxime. Cross-linking improves the rubberproperties, and therefore it manifests better followability when strainoccurs in the component after the paint application, and the retainingstrength at the time of heating also improves.

(3) The inorganic filler used in the first-fourth of the presentinvention is described below.

{circle around (1)} Thermally expandable graphite is a prior artsubstance, and it is prepared by treating powder of natural scalygraphite, heat decomposed graphite, Kish graphite, etc. with aninorganic acid such as concentrated sulfuric acid, nitric acid, andselenic acid, and a strong oxidizing agent such as concentrated nitricacid, perchloric acid, perchlorate, permanganate, dicrhomate, andhydrogen peroxide to produce a graphite inter-layer compound. This is acrystalline compound which maintains the layered structure of carbon.

In the present invention, the thermally expandable graphite obtained bythe aforementioned acid treatment is then neutralized with ammonia, analiphatic lower amine, alkali metal compound, alkali earth metalcompound, etc. Examples of the aliphatic lower amine include monomethylamine, dimethyl amine, trimethyl amine, ethyl amine, propyl amine, andbutyl amine. Examples of the alkali metal compound and the alkali earthmetal compound include hydroxide, oxide, carbonate, sulfate, and organicacid salts of potassium, sodium, calcium, barium, and magnesium.

The particle size of the neutralized thermally expandable graphite ispreferably 20-200 mesh. If the particle size is smaller than 200 mesh,then the degree of expansion of the graphite decreases and an adequatefire-resistant heat insulating layer cannot be obtained. If the particlesize is larger than 20 mesh then, although a larger degree of expansionis effective, dispersion becomes poor when kneading with the resinresulting in reduction of the physical properties.

{circle around (2)} The metal carbonate used for the aforementionedinorganic filler foams at the time of combustion and forms burnedproducts, and therefore is preferable in terms of increasing the shaperetaining properties. Specific examples include calcium carbonate,magnesium carbonate, strontium carbonate, barium carbonate, and zinccarbonate. These can be used independently or in combinations of two ormore.

{circle around (3)} The hydrated inorganic compound used for theaforementioned inorganic filler becomes dehydrated when heated andabsorbs heat, and therefore is preferable in terms of increasing theheat resistance. Specific examples include calcium hydroxide, magnesiumhydroxide, aluminum hydroxide, and hydrotalcite. These can be usedindependently or in combinations of two or more.

A The particle size of the hydrated inorganic compound and the metalcarbonate is preferably 0.5-100 micrometers, and more preferably 1-50micrometers.

When the amounts of the hydrated inorganic compound and the metalcarbonate to be added are small, the dispersibility significantlyinfluences the performance, and therefore a smaller particle size ispreferable. However, if it is less than 0.5 micrometers secondaryaggregation occurs, which worsens the dispersibility. When the amount ofthe hydrated inorganic compound and the metal carbonate to be added islarge, the viscosity increases as more is filled. However, by making theparticle size larger, the increase in the viscosity of thefire-resistant paint can be kept lower, and thus more can be added. Ifit is more than 100 micrometers, then the surface properties of thepaint film and the paint film strength may decrease.

(4) The phosphorus compound used in the second and the fourth inventionis described below.

Selection of the phosphorus compound is not limited in particular.Examples include red phosphorus; various phosphoric esters such astriphenyl phosphate, tricresyl phosphate, trixylenyl phosphate,cresyldiphenyl phosphate, and xylenyl diphenyl phosphate; metalphosphate such as sodium phosphate, potassium phosphate, and magnesiumphosphate; polyammonium phosphate and its derivatives; and the compoundrepresented by the following structural formula (1). Among them,polyammonium phosphate and its derivatives are preferable. Theaforementioned phosphorus compounds can be used independently or incombinations of two or more.

In this formula, R¹ and R³ denote hydrogen, a linear chain or branchedchain alkyl group having 1-16 carbon atoms or an aryl group having 6-16carbon atoms R² denotes a hydroxyl group, a linear chain or branchedchain alkyl group having 1-16 carbon atoms, a linear chain or branchedchain alkoxyl group having 1-16 carbon atoms, an aryl group having 6-16carbon atoms, or an aryloxy group having 6-16 carbon atoms.

For red phosphorus, commercially available red phosphorus can be used.However, in terms of moisture resistance and safety, e.g. prevention ofspontaneous ignition, preferable are those prepared by coating thesurface of red phosphorus particles with resin.

Examples of the polyammonium phosphate and its derivatives includepolyammonium phosphate, and melamine-modified polyammonium phosphate.These are commercially available.

Examples of the compound represented by the aforementioned structuralformula (1) include methylphosphonic acid, dimethyl methylphosphate,diethyl methylphosphate, ethylphosphonic acid, propylphosphonic acid,butylphosphonic acid, 2-methylpropylphosphonic acid, t-butylphosphonicacid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid,phenylphosphonic acid, dioctyiphenyl phosphonate, dimethylphosphinicacid, methylethylphosphinic acid, methylpropylphosphinic acid,diethylphosphinic acid, dioctylphosphinic acid, phenylphosphinic acid,diethylphenyIphosphinic acid, diphenylphosphinic acid, and bis(4-methoxyphenyl) phosphinic acid.

(5) Blend Ratio

{circle around (1)} In the first invention, for the total of 100 weightparts of the epoxy resin and the hardener, the total amount of theinorganic filler, chosen from a group consisting of neutralizedthermally expandable graphite, metal carbonate, and a hydrated inorganiccompound, is 200-500 weight parts. If it is less than 200 weight parts,then adequate fire-resistant performance cannot be obtained. If it ismore than 500 weight parts, then the viscosity increases and a paintform is hard to obtain. Even if painting on the object to be coated ispossible, the mechanical properties of the paint film significantlydecrease and it may not be fit for use. Of the aforementioned totalamount of the inorganic filler, the neutralized thermally expandablegraphite must account for 15-400 weight parts, preferably 50-350 weightparts, and more preferably 100-320 weight parts.

{circle around (2)} In the second invention, for the total of 100 weightparts of the epoxy resin and the hardener, the total amount of thephosphorus compound and the neutralized thermally expandable graphite is15-400 weight parts. If it is less than 15 weight parts, then adequatefire-resistant performance cannot be obtained. If it is more than 400weight parts, then the mechanical properties of the paint filmsignificantly decrease and it may not be fit for use. The preferableamount is 50-350 weight parts, and more preferable is 100-320 weightparts.

The weight ratio between the neutralized thermally expandable graphiteand the phosphorus compound is (thermally expandable graphite/phosphoruscompound)=0.01-9. If the weight ratio is less than 0.01, then theexpansion ratio is insufficient and adequate fire-resistant performancecannot be obtained. If it is more than 9, then the formation of the heatinsulating layer becomes insufficient, reducing the fire-resistantproperties.

The blend ratio of the hydrated inorganic compound and/or metalcarbonate is 10-400 weight parts. If the blend ratio of the hydratedinorganic compound is less than 10 weight parts, then the aforementionedheat absorbing effect of the hydrated inorganic compound does notmanifest adequately. A blend ratio above 400 weight parts results ininsufficient aggregation, which makes it impossible to obtain sufficientpaint film strength. If the blend ratio of the metal carbonate is lessthan 10 weight parts then, as described above, the residual strength isinsufficient. A blend ratio above 400 weight parts results ininsufficient aggregation, which makes it impossible to obtain sufficientpaint film strength and at the same time impedes the expansion duringcombustion, making it impossible to obtain sufficient fire-resistance.

The total amount of the neutralized thermally expandable graphite andphosphorus compound, and the metal carbonate and/or hydrated inorganiccompound is 200-500 weight parts. If the total amount is less than 200weight parts then adequate fire-resistance performance cannot beobtained. If it is more than 500 weight parts then the viscosityincreases and a paint form is hard to obtain. Even if painting on theobject to be coated is possible, the mechanical properties of the paintfilm significantly decrease and it may not be fit for use.

{circle around (3)} In the third invention, for 100 weight parts of thebutyl rubber or isobutylene rubber, the total amount of the inorganicfiller, chosen from a group consisting of neutralized thermallyexpandable graphite, metal carbonate, and a hydrated inorganic compound,is 200-500 weight parts. If it is less than 200 weight parts thenadequate fire-resistance performance cannot be obtained. If it is morethan 500 weight parts then the viscosity increases and a paint form ishard to obtain. Even if painting on the object to be coated is possible,the mechanical properties of the paint film significantly decrease andit may not be fit for use. Of the aforementioned total amount of theinorganic filler, the neutralized thermally expandable graphite mustaccount for 15-400 weight parts, preferably 50-350 weight parts, andmore preferably 100-320 weight parts.

{circle around (4)} In the fourth invention, for the total of 100 weightparts of the butyl rubber or isobutylene rubber, the total amount of thephosphorus compound and the neutralized thermally expandable graphite is15-400 weight parts. If it is less than 15 weight parts, then adequatefire-resistant performance cannot be obtained. If it is more than 400weight parts, then the mechanical properties of the paint filmsignificantly decrease and it may not be fit for use. The preferableamount is 50-350 weight parts, and more preferable is 100-320 weightparts.

The weight ratio between the neutralized thermally expandable graphiteand the phosphorus compound is (thermally expandable graphite/phosphoruscompound)=0.01-9. If the weight ratio is less than 0.01, then theexpansion ratio is insufficient and adequate fire-resistant performancecannot be obtained. If it is more than 9, then the formation of the heatinsulating layer becomes insufficient, reducing the fire-resistantproperties.

The blend ratio of the hydrated inorganic compound and/or metalcarbonate is 10-400 weight parts. If the blend ratio of the hydratedinorganic compound is less than 10 weight parts, then the aforementionedheat absorbing effect of the hydrated inorganic compound does notmanifest adequately. A blend ratio above 400 weight parts results ininsufficient aggregation, which makes it impossible to obtain sufficientpaint film strength. If the blend ratio of the metal carbonate is lessthan 10 weight parts then, as described above, the residual strength isinsufficient. A blend ratio above 400 weight parts results ininsufficient aggregation, which makes it impossible to obtain sufficientpaint film strength and at the same time impedes the expansion duringcombustion, making it impossible to obtain sufficient fire-resistance.

The total amount of the neutralized thermally expandable graphite andphosphorus compound, and the metal carbonate and/or hydrated inorganiccompound is 200-500 weight parts. If the total amount is less than 200weight parts then adequate fire-resistance performance cannot beobtained. If it is more than 500 weight parts then the viscosityincreases and a paint form is hard to obtain. Even if painting on theobject to be coated is possible, the mechanical properties of the paintfilm significantly decrease and it may not be fit for use.

(6) Viscosity

{circle around (1)} The fire-resistant paint which has the compositiondescribed above must have a viscosity, measured by a B type viscometer,of 1-1,000 ps. The fire-resistant paint of the present invention hasgood workability and can be prepared in either a solvent-based or anemulsion-based form. This viscosity can be achieved by adjusting theviscosity-average molecular weight of the epoxy resin, or the butylrubber or isobutylene rubber, the amount of the inorganic filler added,and the amount of the solvent or water. If the viscosity is less than 1ps then sagging occurs on the paint film after application, and if it ismore than 1,000 ps then the viscosity becomes too high and applicationbecomes difficult.

{circle around (2)} In the first and second inventions, it is preferableto adjust the viscosity of the paint by adjusting the viscosity of theepoxy resin or the hardener, rather than using a solvent or water.

In order to adjust the viscosity of the paint via the epoxy resin, anepoxy resin and a hardener which have low viscosities are used. Anexamples of a low-viscosity epoxy resin is bisphenol F type epoxy resin.

An example of the method for adjusting the paint viscosity without usinga solvent or water is a method in which the paint is heated to lower theviscosity. Heating after adding the hardener to the epoxy resin mayresult in hardening before application, therefore it is preferable toheat up the fire-resistant paint of the present invention, and then mixthe hardener into it.

When adjusting the viscosity without using a solvent or water, the totalamount of the inorganic filler is preferably 300 weight parts or lessfor 100 weight parts of the epoxy resin. This is because more than 300weight parts of the inorganic filler makes it difficult to optimallyadjust the viscosity even with the aforementioned method.

{circle around (3)} When a solvent is used to adjust the viscosity,selection of the solvent is not limited in particular. Examples includetoluene and xylene.

A suitable solid content of the fire-resistant paint of the presentinvention, depending on the resin structure, viscosity and molecularweight, is preferably 10-80 wt %, and more preferably 20-70 wt %.

{circle around (4)} When the viscosity is low (1-200 ps), spraying witha spray gun is possible. When the viscosity is higher (200 ps or more),various methods of application such as roller painting become possibleand the application thickness can also be easily set. By changing theapplication thickness, the fire-resistance performance of the object,such as steel bar members, can be determined at will.

(7) Others

Within the range that does not degrade the effect of the presentinvention, a viscosity adjuster, a phenol-based, amine-based, andsulfur-based anti-oxidant, a metal damage preventive agent,anti-electrification agent, stabilizer, cross-linking agent, lubricant,softener, pigment, etc. can be added to the fire-resistant paint of thepresent invention.

The fire-resistant paint of the present invention can be prepared bytreating the ingredients with a prior art kneading and stirringapparatus.

The fire-resistant paint of the first and the second invention is mixedwith the hardener at the time of application to form a fire-resistantcross-linked hardened paint film. The method of hardening the epoxyresin is not limited in particular, and a prior art method can be used.

When the fire-resistant paint of the first and the second invention is asolvent-based paint, the butyl rubber or isobutylene rubber is dissolvedin the solvent, and, after the viscosity adjustment, this can be used asis. In the case of the emulsion-based paint, a common preparation methodis used as well. For example, there is a method in which butyl rubber orisobutylene rubber, dissolved in the solvent, is dispersed in water bymeans of an appropriate emulsifier such asnonylphenoxypolyethoxyethanol-sulfate to obtain a coarse particleemulsion, sheared to particles of 1 micrometer or less for finedispersion, and then the solvent and excess water are removed.

The fire-resistant paint of the present invention, when applied on abase material, forms a fire-resistant paint film. It can be applied witha prior art application method on a base material requiringfire-resistance. There is no particular limitation on how to use thepaint. When it is directly used on a base material requiringfire-resistance, a common primer may be applied first, followed byapplication of the fire-resistant paint on top. A top coating can beadded on top of the fire-resistant paint to improve the appearance andweather resistance.

It is also possible to apply the fire-resistant paint on non-wovenfabric, woven fabric, film, plastic boards, wooden boards, ceramicboards, rockwool boards, plaster boards, metal boards, etc. and then usethese to cover the component requiring fire-resistance.

EXAMPLES

The present invention is described in detail by referring to examplesbelow. The present invention is not limited to these examples. The blendratios in examples are indicated in weight percent units.

(1) Examples Pertaining to the First and the Second Inventions

Examples 1-4, Comparative Examples 1-3

The epoxy resin, hardener, neutralized thermally expandable graphite,polyammonium phosphate, aluminum hydroxide, and calcium carbonate weremixed with the blend ratios shown in Table 1 and kneaded to obtainfire-resistant paint. The obtained fire-resistant paint was applied on a0.3 mm-thick PET film treated for separation and heat-hardened in anoven at 150° C. to prepare a base material sheet coated with thefire-resistant paint with a prescribed thickness which was to be usedfor various evaluations.

<Evaluation of the Heat Insulation>

The base material sheet coated with the fire-resistant paint obtained asdescribed above was cut into 100 mm-long, 100 mm-wide, and 2.0 mm-thicksample pieces. A cone calorimeter (CONE2A from Atlas Electric DevicesCompany) was used to give 50 kW/m² (in the horizontal direction) ofirradiation heating value to the sample pieces for 15 minutes, andfollowing this, those sample pieces with their far side (the heatedsurface is the top side) temperature at 260° C. or lower were defined as◯, and those sample pieces with their far side temperature higher than260° C. were defined as ×. The results are shown in Table 1.

<Evaluation of the Shape Retaining Properties>

The breaking strength of the sample pieces (residue) after theaforementioned fire-resistance evaluation was, measured by using afinger feeling tester (Kato Tech Co., Ltd.).

Measurement Conditions

Compression strength: 0.1 cm/s

Indenter: Flat surface, 0.25 cm²

In the aforementioned measurement, those with a breaking point load from0 to less than 1 kg/cm² are defined as ×, those with a breaking pointload of 1 kg/cm² or more and less than 2.5 kg/cm² are defined as Δ, andthose with a breaking point load of 2.5 kg/cm² or more are defined as ◯.The results are shown in Table 1.

Those with a shape retaining evaluation of Δ or lower are very fragileand collapsed just by setting the sample piece vertically length-wise.Therefore, those will fall off during combustion if they are used as thefire-resistant material in actual use, and they are expected to manifestfire-resistant performance only for a brief period of time.

<Viscosity>

After the preparation, the viscosity of the a paint was measured byusing a B type viscometer (BBH from Tokyo Keiki) at 23° C. with a #5rotor at 1 rpm or 5 rpm.

<Paint Film Strength>

According to JIS K6301, the tensile test was conducted on the samplepieces at a velocity of 200 mm/min, and the elongation at the point ofbreaking (development of a crack) was measured. 20% or more was definedas ◯, and less than 20% was defined as ×. If this elongation is lessthan 20%, cracks develop easily when the component after paintapplication is exposed to a shock or when strain occurs, which leads topartial reduction of the fire-resistace performance. The base materialcoated with the fire-resistant paint obtained as described above waspunched into a dumbbell shape (the parallel section was 10 mm wide and25 mm long, and the thickness was 2 mm) to obtain sample pieces.

<Oxygen Index>

According to JIS K7201, the base material sheet coated with thefire-resistant paint was cut into a sample piece (150 mm long, 60 mmwide, 1 mm thick), which was measured by using an oxygen indexmeasurement apparatus (candle method combustion tester D type from ToyoSeiki Seisaku-sho, Ltd). Those with an oxygen index of 40 or more weredefined as ◯, and those with an oxygen index of less than 40 weredefined as ×.

<Fire-resistance Test>

The fire-resistance test was conducted according to JIS A1304 only onExamples 1 and 4 and Comparative example 2.

Sample piece: Square steel column, 300×300×1200 mm, 12 mm thick

Positions of the thermocouples: each of the four corners and each centerof the four flat surfaces, i.e. a total of eight

The paint was applied on the column such that the thickness would be 2mm, and, after complete hardening, one hour of the fire-resistance testwas conducted. During the test, the temperature of the steel column wasrecorded using the thermocouples, and those with an average steel columntemperature of 350° C. and a maximum of 450° C. or lower were defined as◯.

TABLE 1 Example Comparative example 1 2 3 4 1 2 3 Resin Epoxy resin{circle around (1)} 40 40 — —  40 40  40 Epoxy resin {circle around (2)}— — 63 63 — — — Hardener Diamine-based 60 60 — —  60 60  60 hardener{circle around (1)} Diamine-based — — 37 37 — — — hardener {circlearound (2)} Thermally Thermally 150 50 25 70  30 —  70 expandableexpandable graphite graphite Phosphorus Polyammonium — — 80 100 100 20 —compound phosphate Hydrated Aluminum 150 200 150 100 100 50 200inorganic hydroxide compound Metal Calcium — — — 75 100 50 500 carbonatecarbonate Solvent Xylene 50 25 — 30 — — 100 Evaluation Viscosity (ps)480 640 55 35 Unable 230 380 items to measure Paint film 2 2 2 2 Unable2  2 thickness (mm) to prepare Paint film 120 180 70 40 — 200 Unableelongation (%) to measure Elastic modulus 100 69 245 316 — 48 —(kgf/mm²) Oxygen index ◯ ◯ ◯ ◯ — ◯ ◯ Fire resistance ◯ — — ◯ — × — Heatresistance ◯ ◯ ◯ ◯ — × ×*¹ Shape retaining ◯ ◯ ◯ ◯ — ◯ × properties*¹The residue collapsed.

Epoxy resin {circle around (1)}: Bisphenol F type epoxy resin (viscosity33 ps, Epikote E807 from Yuka Shell Epoxy Kabushiki Kaisha)

Epoxy resin {circle around (2)}: Bisphenol F type epoxy resin (viscosity1.7 ps, Epikote YL6795 from Yuka Shell Epoxy Kabushiki Kaisha)

Diamine-based hardener {circle around (1)}: (viscosity 25 ps, EpikureFL502 from Yuka Shell Epoxy Kabushiki Kaisha)

Diamine-based hardener {circle around (2)}: (viscosity 2.7 ps, EpikureYLH854 from Yuka Shell Epoxy Kabushiki Kaisha)

Thermally expandable graphite: Neutralized thermally expandable graphite(80 mesh, Flamecut GREP-EG from Tosoh Corporation)

Polyammonium phosphate (EXOLIT AP422 from Clariant GmbH)

Aluminum hydroxide: (average particle diameter 18 micrometers, HigiliteH-31 from Showa Denko, K.K.)

Calcium carbonate: (average particle diameter 8 micrometers, BF-300 fromBihoku Funka Kogyo Co., Ltd.)

Table 1 indicates that the fire-resistant paint of Examples havesuperior fire-resistance performance, heat insulating performance, andshape retaining properties.

(2) Examples Pertaining to the Third and the Fourth Inventions

Examples 5-10, Comparative Examples 4-8

The ingredients shown in Table 2 and Table 3 were added to the solvent,the inorganic filler was then stirred in with a mixer and dissolved anddispersed to prepare a fire-resistant paint.

Prepared paint (A) was used as such to carry out evaluation 1.

Prepared paint (A) was applied on a galvanized steel plate with an areaof 10×10 cm and a thickness of 0.3 mm such that the paint film thicknesswould be the required value, and dried in a 80° C. oven to obtain samplepiece (B), which was used to carry out. evaluations 2, 3, 6, 8, and 9.

Prepared paint (A) was applied on a 0.3 mm-thick PET film treated forseparation such that the paint film thickness would be the requiredvalue, and dried in a 80° C. oven. Then the film was peeled to obtainsample piece (C), which was used to carry out evaluations 4, 5, and 10.

Prepared paint (A) was sprayed on a 0.3 mm-thick iron plate such thatthe paint film thickness would be 2 mm, and dried in a 80° C. oven toobtain sample piece (D), which was used to carry out fire-resistancetest 7.

1. Viscosity

After the preparation, the viscosity at 23° C. of the paint was measuredby using a B type viscometer (BBH from Tokyo Keiki) with a #4 rotor at 1rpm.

2. Expansion Ratio

Sample piece (B) which had a 2.0 mm-thick paint film was placed on acone calorimeter (CONE2A from Atlas Electric Devices Company) with theirradiation heating value set at 50 kW/m², and, after it was completelyburned in the horizontal position, the residue was removed to measurethe expansion ratio of the residue after expansion. The expansion ratiowas calculated using the following equation.

Expansion ratio (times)=Residue thickness after heating/Sheet thicknessbefore heating

3. Residue Strength

Sample piece (B) which had a 2.0 mm-thick paint film was placed on acone calorimeter (CONE2A from Atlas Electric Devices Company) with theirradiation heating value set at 50 kW/m , and, after it was completelyburnt in the horizontal position, the residue was removed to measure thestrength of the residue after combustion by using a finger feelingtester (Kato Tech Co., Ltd.).

Using a 25 cm² indenter at a velocity of 0.1 cm/sec, the residue wascompressed and the first maximum in the strain-stress curve was definedas the strength at which the residue ruptures (=residue strength).

4. Oxygen Index

According to JIS K7201, the testing sheet coated with the fire-resistantpaint was cut into a sample piece (150 mm long, 60 mm wide, 1 mm thick),which was measured using an oxygen index measurement apparatus (candlemethod combustion tester D type from Toyo Seiki Seisaku-sho, Ltd).

5. Paint Film Strength

According to JIS K6301, the tensile test was conducted on the #2dumbbell shape sample piece punched out from (C) (the parallel sectionwas 10 mm wide and 25 mm long, and the thickness was 2 mm) at a velocityof 200 mm/min, and the elongation at the point of breaking (developmentof a crack) was measured.

If this elongation is small, cracks develop easily when the componentafter paint application is exposed to a shock or when strain occurs,which leads to partial reduction of the fire-resistace performance.

6. Heat Insulation Test

A cone calorimeter (CONE2A from Atlas Electric Devices Company) was usedto give 50 kW/m² (in the horizontal direction) of irradiation heatingvalue to sample piece B with a paint film thickness of 2.0 mm for 15minutes, and following this, those sample pieces with their far side(the heated surface is the top side) temperature at 260° C. or lowerwere defined as ◯ and those sample pieces with their far sidetemperature higher than 260° C. were defined as ×.

7. Fire-resistance Test

The fire-resistance test was conducted as described below according toJIS A1304.

Sample piece: Square steel column, 300×300×1200 mm, 12 mm thick

Positions: of the thermocouples: each of the four corners and eachcenter of the four flat surfaces, i.e. a total of eight.

The column was covered with sample piece B with a paint film thicknessof 2.0 mm, and the temperature of the steel column was recorded by usingthe thermocouples.

Those with an average steel column temperature of 350° C. or lower and amaximum of 450° C. or lower (JIS A1304 compliant level) were defined as◯.

8. Elution-to-water Test

Sample piece B with a paint film thickness of 2.0 mm was soaked in waterat 23° C. for one hour, and, after drying at 100° C., the weightreduction ratio was measured to calculate the degree of elution.

Degree of elution (%)=(Sheet weight before soaking−Sheet weight aftersoaking)/Sheet weight before soaking

9. Existence of Cracks Caused by Nailing

A nail was hammered into the center of sample piece B with a paint filmthickness of 2.0 mm, and the area around the nail head was checked forcracks.

10.Adhesive Properties of the Paint Film

According to JIS Z 0237, sample piece C with a paint film thickness of2.0 mm was cut into 2.5 cm wide strips, pasted on a galvanized ironsheet, and, after an hour, peeled off the sheet at a velocity of 300mm/min in the 90 degree direction to measure the peeling strength.

TABLE 2 Example 5 6 7 8 9 10 Resin Butyl rubber 100 100 100 Isobutylenerubber {circle around (1)} 100 100 Isobutylene rubber {circle around(2)} 100 Acrylic resin {circle around (1)} Acrylic resin {circle around(2)} Thermally Thermally expandable 150 30 30 80 300 50 expandablegraphite {circle around (1)} graphite Thermally expandable graphite{circle around (2)} Thermally expandable graphite {circle around (3)}Phosphorus Polyammonium phosphate {circle around (1)} 100 90 150compound Polyammonium phosphate {circle around (2)} 50 Polyammoniumphosphate {circle around (3)} Red phosphorus 10 Hydrated Aluminumhydroxide 50 50 100 100 50 20 inorganic Magnesium hydroxide 20 compoundMetal Calcium carbonate 100 100 100 130 30 carbonate Strontium carbonate20 Others Polybutene 10 Tackifier 45 Vermiculite 20 MelamineDipentaerythritol Titanium dioxide Solvent Toluene 800 1000 650 600 2000250 Xylene 500 Solid content (wt %) 33 29 29 49 18 50 Viscosity (ps) 300250 200 600 100 400 Evaluation Expansion ratio (times) 25.0 10.2 10.013.0 48.0 11.0 items Residue strength (kg/cm²) 0.04 1.70 1.10 0.80 0.010.70 Fire resistance ◯ ◯ ◯ ◯ ◯ ◯ Maximum temperature (° C.) in 335 350355 340 330 340 the fire-resistance test Average temperature (° C.) in315 330 330 330 310 320 the fire-resistance test Heat insulation ◯ ◯ ◯ ◯◯ ◯ Oxygen index 45 44 48 50 40 40 Paint film strength 250 300 220 110220 280 (elongation %) Elastic modulus (kgf/mm²) 1.6 1.0 1.5 1.8 1.5 1.2Elution to water (%) 0.05 0.1 0.1 0.1 0.05 0.08 Cracks caused by nailingNot Not Not Not Not Not observed observed observed observed observedobserved Peeling strength (gf/25 mm) 650 600 700 500 650 700

TABLE 3 Comparative Example 4 5 6 7 8 Resin Butyl rubber 100 Isobutylenerubber {circle around (1)} 100 Isobutylene rubber {circle around (2)}100 Acrylic resin {circle around (1)} 80 80 Acrylic resin {circle around(2)} 20 20 Thermally Thermally expandable 5 600 expandable graphite{circle around (1)} graphite Thermally expandable 25 graphite {circlearound (2)} Thermally expandable 25 graphite {circle around (3)}Phosphorus Polyammonium phosphate {circle around (1)} 100 compoundPolyammonium phosphate {circle around (2)} Polyammonium phosphate{circle around (3)} 200 200 Red phosphorus Hydrated Aluminum hydroxideinorganic Magnesium hydroxide compound Metal Calcium carbonate carbonateStrontium carbonate 20 Others Polybutene Tackifier Vermiculite Melamine60 60 Dipentaerythritol 60 Titanium dioxide 80 80 Solvent Toluene 800160 200 1000 1000 Xylene Solid content (wt %) 12 90 50 34 32 Viscosity(ps) 80 *2 450 400 370 Evaluation Expansion ratio (times) 5.2 55 5 4 6items Residue strength (kg/cm²) 0.01 0.01 *4 0.5 0.01 Fire resistance ×◯ × × × Maximum temperature (° C.) in 950 *3 960 930 480 thefire-resistance test Average temperature (° C.) in 800 *3 780 780 360the fire-resistance test Heat insulation × ◯ × × × Oxygen index *1 *3 3848 50 Paint film strength 290 Unable 300 80 160 (elongation %) tomeasure Elastic modulus (kgf/mm²) 0.9 Unable 0.9 2.2 2.0 to measureElution to water (%) 0.05 0.05 0.1 1 0.1 Cracks caused by nailing NotNot Not Observed Observed observed observed observed Peeling strength(gf/25 mm) 750 Unable 500 *5 *6 to measure

Butyl rubber: Flory's viscosity-average molecular weight 450.000, tradename “Exxonbutyl 165” (from Exxon Chemical Ltd.)

Isobutylene rubber {circle around (1)}: Flory's viscosity-averagemolecular weight 11,000, trade name “VISTANEX LM-MH” (from ExxonChemical Ltd.)

Isobutylene rubber {circle around (2)}: Flory's viscosity-averagemolecular weight 2,100,000, trade name “VISTANEX MML-140” (from ExxonChemical Ltd.)

Acrylic {circle around (1)}: Trade name “Priolite AC80” (from GoodyearChemical Co., Ltd.)

Acrylic {circle around (2)}: Trade name “Priolite AC4” (from GoodyearChemical Co., Ltd.)

Polybutene: Trade name “H-1900” (from Amoco Co., Ltd.), weight-averagemolecular weight 2270 Tackifier: Trade name “Escorez 1102B” (from TonexCo. , Ltd.)

Polyammonium phosphate {circle around (1)}: Trade name “EXOLIT AP422”(from Clariant GmbH), average particle diameter 15 micrometers

Polyammonium phosphate {circle around (2)}: Trade name “Terraju C80”(from Chisso Corporation), average particle diameter 15-25 micrometers

Polyammonium phosphate {circle around (3)}: Trade name “EXOLIT AP462”(from Clariant GmbH), average particle diameter 15 micrometers

Red phosphorus: Trade name “EXOLIT RP 605” (from Clariant GmbH), averageparticle diameter 30-40 micrometers

Thermally expandable graphite {circle around (1)}: Trade name “FlamecutGREP-EG” (from Tosoh Corporation) (expansion initiation temperature=200°C.) 80 mesh

Thermally expandable graphite {circle around (2)}: Trade name“Expandable Graphite No. 8099” (from Chuo Kasei Co., Ltd.) (expansioninitiation temperature=500° C.) 60 mesh

Thermally expandable graphite {circle around (3)}: Trade name“Expandable Graphite No. 8099-LTE-u” (from Chuo Kasei Co., Ltd.)(expansion initiation temperature=200° C.) 60 mesh

Vermiculite: Trade name “Vermiculite” 60 mesh (Kinsei Matec Co., Ltd.)

Aluminum hydroxide: Trade name “Higilite H-31” (Showa Denko, K.K.) 18micrometers

Magnesium hydroxide: Trade name “Kisuma 5B” (from Kyowa ChemicalIndustry Co., Ltd.) average particle diameter 1.9 micrometers

Calcium carbonate: Trade name “BF300” (from Bihoku Funka Kogyo Co.,Ltd.) average particle diameter 8 micrometers

Strontium carbonate: (from Sakai Chemical Industry Co., Ltd.) averageparticle size 1.2 micrometers

Melamine: from Wako Pure Chemical Industries, Ltd.

Dipentaerythritol: Trade name “D-PE (Dipentaerythritol) 300M” (from KoeiChemical Co., Ltd.) 300 mesh, average particle size 5 micrometers

Titanium dioxide: Trade name “Tipaque CR95” (from Ishihara SangyoKaisha, Ltd.)

Notes on the parts in the table marked with *.

Comparative Example 4

*1) When the oxygen index measurement jig was mounted, sagging occurred,which made accurate measurement impossible.

Comparative Example 5

*2) Not viscous but crumbly. The viscosity measurement was not possible.

*3) When the oxygen index measurement jig was mounted, crumblingoccurred from the edge, which made accurate measurement impossible.

*3′) Not tested because the paint thickness could not be made even.

Comparative Example 6

*4) Expansion did occur. However, it was expansion of only a thin skinon the surface and deflated when touched by something, making itimpossible to measure the residue strength.

Comparative Example 7

*5) Since the expansion ratio was not sufficient, the heat insulationwas not sufficient and therefore did not pass the fire-resistance test.Since the paint film had significant elution and water resistance waspoor, a top coating would be necessary.

Comparative Example 8

*6) Since polyhydric alcohol was not contained, the water resistance wasadequate. However, the residue was fragile and the expansion ratio wasinsufficient, and therefore it did not pass the fire-resistance test.

Table 2 indicates that the fire-resistant paint of Examples havesuperior fire-resistance performance, heat insulation performance, andshape retaining properties.

INDUSTRIAL APPLICABILITY OF THE INVENTION

The fire-resistant paint of the present invention has particularlyremarkable fire resistance, and can be used in a wide range ofapplications.

What is claimed is:
 1. A fire-resistant paint containing an epoxy resin,a hardener, and an inorganic filler wherein {circle around (1)} for thetotal of 100 weight parts of the epoxy resin and the hardener, {circlearound (2)} 200-500 weight parts of the inorganic filler, selected fromthe group consisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound; {circle around (3)} forthe inorganic filler, at least 15-400 weight parts of neutralizedthermally expandable graphite; and {circle around (4)} the viscosity ofthe fire-resistant paint is 1-1,000 ps as measured by a B-typeviscometer, said neutralized thermally expandable graphite having aparticle size of 20-200 mesh.
 2. A fire-resistant paint containing butylrubber or isobutylene rubber and an inorganic filler wherein {circlearound (1)} Flory's viscosity-average molecular weight of the butylrubber or isobutylene rubber is 5,000-4,000,000; and {circle around (2)}for 100 weight parts of the butyl rubber or isobutylene rubber, {circlearound (3)} 200-500 weight parts of the inorganic filler, chosen from agroup consisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound is contained; {circlearound (4)} for the inorganic filler, at least 15-400 weight parts ofneutralized thermally expandable graphite is contained; and {circlearound (5)} the viscosity of the fire-resistant paint is 1-1,000 ps asmeasured by a B-type viscometer.
 3. A fire-resistant paint containingbutyl rubber or isobutylene rubber and an inorganic filler wherein{circle around (1)} Flory's viscosity-average molecular weight of thebutyl rubber or isobutylene rubber is 5,000-4,000,000; and {circlearound (2)} for 100 weight parts of the butyl rubber or isobutylenerubber, {circle around (3)} 15-400 weight parts of neutralized thermallyexpandable graphite and a phosphorus compound is contained; {circlearound (4)} the weight ratio between the neutralized thermallyexpandable graphite and the phosphorus compound is (thermally expandablegraphite/phosphorus compound)=0.01-9; {circle around (5)} 10-400 weightparts of a metal carbonate and/or hydrated inorganic compound iscontained; {circle around (6)} the total amount of the neutralizedthermally expandable graphite and phosphorus compound, and the metalcarbonate and/or hydrated inorganic compound is 200-500 weight parts;and {circle around (7)} the viscosity. of the fire-resistant paint is1-1,000 ps as measured by a B-type viscometer.
 4. A fire-resistant paintcontaining an epoxy resin, a hardener, and an inorganic filler wherein{circle around (1)} with a total of 100 weight parts of the epoxy resinand the hardener, {circle around (2)} there is contained 15-400 weightparts of neutralized thermally expandable graphite and a phosphoruscompound; {circle around (3)} the weight ratio between the neutralizedthermally expandable graphite and the phosphorus compound is (thermallyexpandable graphite/phosphorus compound)=0.01-9; {circle around (4)}there is contained 10-400 weight parts of a metal carbonate and/orhydrated inorganic compound; {circle around (5)} the total amount of theneutralized thermally expandable graphite and phosphorus compound, andthe metal carbonate and/or hydrated inorganic compound is 200-500 weightparts; {circle around (6)} the viscosity of the fire resistant paint is1-1,000 Ps as measured by a B-type viscometer; and {circle around (7)}wherein the average particle size of said neutralized thermallyexpandable graphite is 20-200 mesh.
 5. A fire-resistant paint containingan epoxy resin, a hardener, and an inorganic filler wherein {circlearound (1)} for the total of 100 weight parts of the epoxy resin and thehardener, {circle around (2)} 200-500 weight parts of an inorganicfiller selected from the group consisting of neutralized thermallyexpandable graphite, metal carbonate, and a hydrated inorganic compound;{circle around (3)} for the inorganic filler, at least 15-400 weightparts of neutralized thermally expandable graphite; and {circle around(4)} the viscosity of the fire-resistant paint is 1-1,000 ps as measuredby a B-type viscometer, said metal carbonate being one or more metalcarbonates selected from the group consisting of calcium carbonate,magnesium carbonate, strontium carbonate, barium carbonate and zinccarbonate.
 6. The fire-resistant paint of claim 5, wherein said hydratedinorganic compounds are selected from the group consisting of calciumhydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite. 7.A fire-resistant paint containing an epoxy resin, a hardener, and aninorganic filler wherein {circle around (1)} for the total of 100 weightparts of the epoxy resin and the hardener, {circle around (2)} 200-500weight parts of the inorganic filler, selected from the group consistingof neutralized thermally expandable graphite, metal carbonate, and ahydrated inorganic compound; {circle around (3)} for the inorganicfiller, at least 15-400 weight parts of neutralized thermally expandablegraphite; and {circle around (4)} the viscosity of the fire-resistantpaint is 1-1,000 ps as measured by a B-type viscometer, wherein saidfire-resistant paint is a no-solvent paint.
 8. The fire-resistant paintof claim 2 wherein said fire-resistant paint is a solvent-based oremulsion-based paint containing an organic solvent or water.
 9. Afire-resistant paint-coated base material coated with the paint film byapplying the fire-resistant paint of claim 1 on the base material.
 10. Abase material coated with a fire-resistant paint containing an epoxyresin, a hardener, and an inorganic filler wherein {circle around (1)}for the total of 100 weight parts or the epoxy resin and the hardener,{circle around (2)} 200-500 weight parts of the inorganic filler,selected from the group consisting of neutralized thermally expandablegraphite, metal carbonate, and a hydrated inorganic compound; {circlearound (3)} for the inorganic filler, at least 15-400 weight parts ofneutralized thermally expandable graphite; and {circle around (4)} theviscosity of the fire-resistant paint is 1-1,000 ps as measured by aB-type viscometer, said base material being non-woven fabric, wovenfabric, film, plastic board, wooden board, ceramic board, rockwoolboard, plaster board, or metal boar.
 11. A base material coated with afire-resistant paint of claim
 4. 12. The fire-resistant paint of claim 2wherein the average particle size of said neutralized thermallyexpandable graphite is 20-200 mesh.
 13. The fire-resistant paint ofclaim 3 wherein the average particle size of said neutralized thermallyexpandable graphite is 20-200 mesh.
 14. A fire-resistant paintcontaining an epoxy resin, a hardener, and an inorganic filler wherein{circle around (1)} for the total of 100 weight parts of the epoxy resinand the hardener, {circle around (2)} 15-400 weight parts of neutralizedthermally expandable graphite and a phosphorus compound; {circle around(3)} the weight ratio between the neutralized thermally expandablegraphite and the phosphorus compound is (thermally expandablegraphite/phosphorus compound)=0.01-9; {circle around (4)} 10-400 weightparts of a metal carbonate and/or hydrated inorganic compound; {circlearound (5)} the total amount of the neutralized thermally expandablegraphite and phosphorus compound, and the metal carbonate and/orhydrated inorganic compound is 200-500 weight parts; and {circle around(6)} the viscosity of the fire-resistant paint is 1-1,000 ps as measuredby a B-type viscometer, wherein said metal carbonate is one or moremetal carbonates selected from the group consisting of calciumcarbonate, magnesium carbonate, strontium carbonate, barium carbonateand zinc carbonate.
 15. A fire-resistant paint containing butyl rubberor isobutylene rubber and an inorganic filler wherein {circle around(1)} Flory's viscosity-average molecular weight of the butyl rubber orisobutylene rubber is 5,000-4,000,000; and {circle around (2)} for 100weight parts of the butyl rubber or isobutylene rubber, {circle around(3)} 200-500 weight parts of the inorganic filler, selected from thegroup consisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound; {circle around (4)} forthe inorganic filler, at least 15-400 weight parts of neutralizedthermally expandable graphite; and the viscosity of the fire-resistantpaint is 1-1,000 ps as measured by a B-type viscometer, wherein saidmetal carbonate is one or more metal carbonates selected from the groupconsisting of calcium carbonate, magnesium carbonate, strontiumcarbonate, barium carbonate and zinc carbonate.
 16. The fire-resistantpaint of claim 3, wherein said metal carbonate is one ore more metalcarbonates chosen from among the group consisting of calcium carbonate,magnesium carbonate, strontium carbonate, barium carbonate and zinccarbonate.
 17. A fire-resistant paint containing an epoxy resin, ahardener, and an inorganic filler wherein {circle around (1)} for thetotal of 100 weight parts of the epoxy resin and the hardener, {circlearound (2)} 200-500 weight parts of the inorganic filler, selected fromthe group consisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound; {circle around (3)} forthe inorganic filler, at least 15-400 weight parts of neutralizedthermally expandable graphite; and {circle around (4)} the viscosity ofthe fire-resistant paint is 1-1,000 ps as measured by a B-typeviscometer, wherein the average particle size of said neutralizedthermally expandable graphite 20-200 mesh, and carbonate is one or moremetal carbonates selected from the group consisting of calciumcarbonate, magnesium carbonate, strontium carbonate, barium carbonateand zinc carbonate.
 18. A fire-resistant paint containing an epoxyresin, a hardener, and an inorganic filler wherein {circle around (1)}for the total of 100 weight parts of the epoxy resin and the hardener,{circle around (2)} 15-400 weight parts of neutralized thermallyexpandable graphite and a phosphorus compound; {circle around (3)} theweight ratio between the neutralized thermally expandable graphite andthe phosphorus compound is (thermally expandable graphite/phosphoruscompound)=0.01-9; {circle around (4)} 10-400 weight parts of a metalcarbonate and/or hydrated inorganic compound; {circle around (5)} thetotal amount of the neutralized thermally expandable graphite andphosphorus compound, and the metal carbonate and/or hydrated inorganiccompound is 200-500 weight parts; and {circle around (6)} the viscosityof the fire-resistant paint is 1-1,000 ps as measured by a B-typeviscometer, wherein said hydrated inorganic compounds are selected fromthe group consisting of calcium hydroxide, magnesium hydroxide, aluminumhydroxide, and hydrotalcite.
 19. The fire-resistant paint of claim 2,wherein said hydrated inorganic compounds are chosen from among thegroup consisting of calcium hydroxide, magnesium hydroxide, aluminumhydroxide, and hydrotalcite.
 20. The fire-resistant paint of claim 3,wherein said hydrated inorganic compounds are chosen from among thegroup consisting of calcium hydroxide, magnesium hydroxide, aluminumhydroxide, and hydrotalcite.
 21. A fire-resistant paint containing anepoxy resin, a hardener, and an inorganic filler wherein {circle around(1)} for the total of 100 weight parts of the epoxy resin and thehardener, {circle around (2)} 200-500 weight parts of the inorganicfiller, selected from the group consisting of neutralized thermallyexpandable graphite, metal carbonate, and a hydrated inorganic compound;{circle around (3)} for the inorganic filler, at least 15-400 weightparts of neutralized thermally expandable graphite; and {circle around(4)} the viscosity of the fire-resistant paint is 1-1,000 ps as measuredby a B-type viscometer, said metal carbonate being one or more metalcarbonates selected from the group consisting of calcium carbonate,magnesium carbonate, strontium carbonate, barium carbonate and zinccarbonate, wherein said hydrated inorganic compounds are selected fromthe group consisting of calcium hydroxide, magnesium hydroxide, aluminumhydroxide, and hydrotalcite.
 22. A base material coated with afire-resistant paint containing an epoxy resin, a hardener, and aninorganic filler wherein {circle around (1)} for the total of 100 weightparts of the epoxy resin and the hardener, {circle around (2)} 15-400weight parts of neutralized thermally expandable graphite and aphosphorus compound; {circle around (3)} the weight ratio between theneutralized thermally expandable graphite and the phosphorus compound is(thermally expandable graphite/phosphorus compound)=0.01-9; {circlearound (4)} 10-400 weight parts of a metal carbonate and/or hydratedinorganic compound; {circle around (5)} the total amount of theneutralized thermally expandable graphite and phosphorus compound, andthe metal carbonate and/or hydrated inorganic compound is 200-500 weightparts; and {circle around (6)} the viscosity of the fire-resistant paintis 1-1,000 ps as measured by a B-type viscometer.
 23. A fire-resistantpaint-coated base material coated with the paint film by applying thefire-resistant paint of claim 2 on the base material.
 24. Afire-resistant paint-coated base material coated with the paint film byapplying the fire-resistant paint of claim 3 on the base material.
 25. Abase material coated with a fire-resistant paint containing an epoxyresin, a hardener, and an inorganic filler wherein {circle around (1)}for the total of 100 weight parts of the epoxy resin and the hardener,{circle around (2)} 200-500 weight parts of the inorganic filler,selected from group consisting of neutralized thermally expandablegraphite, metal carbonate, and a hydrated inorganic compound; {circlearound (3)} for the inorganic filler, at least 15-400 weight parts ofneutralized thermally expandable graphite; and {circle around (4)} theviscosity of the fire-resistant paint is 1-1,000 ps as measured by aB-type viscometer, wherein the average particle size of said neutralizedthermally expandable graphite is 20-200 mesh.
 26. A base material coatedwith a fire-resistant paint containing an epoxy resin, a hardener, andan inorganic filler wherein {circle around (1)} for the total of 100weight parts of the epoxy resin and the hardener, {circle around (2)}200-500 weight parts of the inorganic filler, selected from the groupconsisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound; {circle around (3)} forthe inorganic filler, at least 15-400 weight parts of neutralizedthermally expandable graphite; and {circle around (4)} the viscosity ofthe fire-resistant paint is 1-1,000 ps as measured by a B-typeviscometer, said metal carbonate being one or more metal carbonatesselected from the group consisting of calcium carbonate, magnesiumcarbonate, strontium carbonate, barium carbonate and zinc carbonate. 27.A base material coated with a fire-resistant paint containing an epoxyresin, a hardener, and an inorganic filler wherein {circle around (1)}for the total of 100 weight parts of the epoxy resin and the hardener,{circle around (2)} 200-500 weight parts of the inorganic filler,selected from the group consisting of neutralized thermally expandablegraphite, metal carbonate, and a hydrated inorganic compound; {circlearound (3)} for the inorganic filler, at least 15-400 weight parts ofneutralized thermally expandable graphite is contained; and {circlearound (4)} the viscosity of the fire-resistant paint is 1-1,000 ps asmeasured by a B-type viscometer, wherein said hydrated inorganiccompounds are selected from the group consisting of calcium hydroxide,magnesium hydroxide, aluminum hydroxide, and hydrotalcite.
 28. A basematerial coated with a fire-resistant paint containing an epoxy resin, ahardener, and an inorganic filler wherein {circle around (1)} for thetotal of 100 weight parts of the epoxy resin and the hardener, {circlearound (2)} 200-500 weight parts of the inorganic filler, selected fromthe group consisting of neutralized thermally expandable graphite, metalcarbonate, and a hydrated inorganic compound is contained; {circlearound (3)} for the inorganic filler, at least 5-400 weight parts ofneutralized thermally expandable graphite; and {circle around (4)} theviscosity of the fire-resistant paint is 1-1,000 ps as measured by aB-type viscometer, wherein said fire-resistant paint is a no-solventpaint.
 29. A fire-resistant paint-coated base material coated with thepaint film by applying the fire-resistant paint of claim 8 on the basematerial.
 30. A fire-resistant paint containing an epoxy resin, ahardener, and an inorganic filler wherein {circle around (1)} for thetotal of 100 weight parts of the epoxy resin and the hardener, {circlearound (2)} 15-400 weight parts of neutralized thermally expandablegraphite and a phosphorus compound; {circle around (3)} the weight ratebetween the neutralized thermally expandable graphite and the phosphoruscompound is (thermally expandable graphite/phosphorus compound)=0.01-9;{circle around (4)} 10-400 weight parts of a metal carbonate and/orhydrated inorganic compound; {circle around (5)} the total amount of theneutralized thermally expandable graphite and phosphorus compound, andthe metal carbonate and/or hydrated inorganic compound is 200-500 weightcars; and {circle around (6)} the viscosity of the fire-resistant paintis 1-1,000 ps as measured by a B-type e, and wherein said fire-resistantpaint as a no-solvent paint.
 31. The fire-resistant paint of claim 3,wherein said fire-resistant paint is a solvent-based or emulsion-basedpaint containing an organic solvent or water.